CN112850756A - Method for extracting and preparing high-purity anhydrous lithium sulfate solid from byproduct mirabilite of lithium smelting enterprise - Google Patents
Method for extracting and preparing high-purity anhydrous lithium sulfate solid from byproduct mirabilite of lithium smelting enterprise Download PDFInfo
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Abstract
The invention provides a method for extracting and preparing high-purity anhydrous lithium sulfate solid from mirabilite which is a byproduct of a lithium smelting enterprise, and belongs to the field of lithium recovery. The method comprises the following steps: 1) dissolving a first organic solvent; 2) washing with pure water; 3) circulating; 4) evaporating and concentrating; 5) crystallizing; 6) and (5) spray drying. In the method, the raw material source for preparing the product is the byproduct mirabilite of a lithium smelting enterprise, high-purity anhydrous lithium sulfate solid is extracted and prepared from the mirabilite, and all solvents can be continuously used in the circulating process. The technical scheme has the characteristics of simplicity, feasibility, low energy consumption, no influence on product quality, no three-waste discharge, no pollution to environment, good economic and social benefits and the like, is not added with other precipitating agents, and can effectively carry out comprehensive recovery of lithium resources.
Description
Technical Field
The invention relates to the field of lithium recovery, in particular to a method for extracting and preparing high-purity anhydrous lithium sulfate solid from mirabilite which is a byproduct of a lithium smelting enterprise.
Background
Lithium is an important strategic resource, and with the rapid development of low-carbon economy and green new energy industry, particularly with the breakthrough and popularization and application of high-capacity power battery technology, the novel lithium electric vehicle industry rises rapidly, and the rapid development of the lithium electric industry becomes a common consensus of people. With the emergence of the national new energy development plan, the lithium battery new energy becomes one of the energy industries which are key in national support development; lithium is an important basic element for the development of new energy of lithium batteries, and the market price is continuously increased due to scarcity and increasingly large demand. Therefore, comprehensive recovery and recycling of lithium resources become a hot point of current research.
In the current lithium smelting enterprises, no matter lepidolite or spodumene is used as a raw material, a large amount of sodium ions are inevitably enriched in the production process in the circulating production due to the process, and the quality of the final lithium salt product is influenced by the sodium ions with too high concentration. Therefore, most of the current enterprises practice to freeze and crystallize the lithium-containing solution with high concentration of sodium ions, and separate out mirabilite solid which is sold as a byproduct. However, the process has the disadvantage that a certain amount of lithium (calculated by metallic lithium, the content is 0.2-1%) is carried in the mirabilite which is a byproduct, so that a large amount of lithium resources are lost and wasted.
With the vigorous development of the lithium battery new energy industry, the domestic lithium salt production capacity and the lithium salt yield rapidly climb, the lithium carbonate yield of 25 ten thousand tons per year is achieved at present, and a large amount of byproduct mirabilite corresponds to the lithium carbonate yield. If the lithium carried in the mirabilite can not be effectively extracted and recovered, the serious lithium resource loss can be caused.
From reported literature data, no method for extracting and preparing high-purity lithium sulfate from mirabilite which is a byproduct of lithium smelting enterprises is involved.
Disclosure of Invention
Aiming at the current situation and the technical blank, the invention aims to provide a method for recovering and extracting high-purity lithium sulfate solid from mirabilite which is a byproduct of a lithium smelting enterprise. In order to fill up the technical blank, the inventor conducts a large number of experiments, and tries to recover lithium sulfate from mirabilite by a plurality of organic solvents, the target effect cannot be achieved, some solvents cannot recover lithium sulfate from mirabilite, and the purity of lithium sulfate prepared by some solvents is too low. The inventor unexpectedly finds that the mixture of dichloromethane, petroleum ether and n-butanol can effectively recover lithium sulfate from mirabilite after a large number of experiments, successfully overcomes the technical difficulty, and fills up the technical blank in the field. The method of the invention abandons the traditional repeated impurity removal step, simplifies the process flow, can recycle the solvent and has higher product recovery rate and purity.
The method realizes the purpose of comprehensively recovering lithium resources, has good economic effect, can save resources and protect the environment, and has good social benefit.
In order to achieve the aim, the invention provides a method for extracting and preparing high-purity anhydrous lithium sulfate solid from mirabilite which is a byproduct of a lithium smelting enterprise, which comprises the following steps:
s1, dissolving: adding mirabilite and a first organic solvent into a container, fully stirring, performing solid-liquid separation by using a filtering device, respectively collecting a solid phase and a liquid phase, wherein the liquid phase is an organic phase containing lithium sulfate, the solid phase is wet mirabilite, and drying the wet mirabilite.
Wherein the first organic solvent is a mixture of dichloromethane, petroleum ether and n-butanol, wherein the content of dichloromethane is in the range of 40% -70%, the content of petroleum ether is in the range of 30% -60%, and the content of n-butanol is in the range of 5% -40%. Preferably, the mixture has a dichloromethane content of 60%, a petroleum ether content of 30%, and n-butanol content ranging from 10%.
Preferably, the solid-to-liquid ratio of the mirabilite to the first organic solvent is in the range of 1:1 to 1: 3.
Preferably, the solid-liquid separation equipment is selected from a plate frame filter, a centrifuge or a vacuum filtration bottle.
Preferably, the dried mirabilite is sold as a byproduct and can be used in the fields of detergents, sodium sulfide, paper pulp, artificial fiber, glass industry and the like.
S2, washing: washing: and (4) injecting deionized water into the liquid phase obtained in the step (S1), standing, and separating by using an oil-water separation device to obtain a water phase and an organic phase containing lithium sulfate respectively.
Preferably, the oil-water separation equipment is selected from a centrifugal oil-water separator, a vacuum filtration oil-water separator or a separating funnel.
S3, circulating: repeating steps S1 and S2, wherein the organic phase obtained in step S2 is used to replace the first organic solvent and the aqueous phase containing lithium sulfate obtained in step S2 is used to replace the first organic solventThe deionized water is used for repeating the steps until Li in the water phase containing lithium sulfate+When the concentration does not increase any more, the next step is carried out.
Preferably, Li in the aqueous phase when containing lithium sulfate+When the concentration reaches the range of 5-10g/L, the next step is carried out.
S4, evaporation and concentration: and (4) heating, evaporating and concentrating the aqueous phase containing the lithium sulfate finally obtained in the step (S3) by using an evaporation device to obtain a high-concentration lithium sulfate solution.
Preferably, the evaporation apparatus is selected from a triple effect evaporator, MVR or hot plate.
Optionally, the temperature for heating, evaporating and concentrating is 70-105 ℃.
Preferably, the aqueous phase containing lithium sulphate is concentrated by evaporation to a lithium content of 15-28 g/L.
More preferably, the aqueous phase containing lithium sulphate is concentrated by evaporation to a lithium content of 23 g/L.
S5, crystallizing: and (4) adding a second organic solvent into the high-concentration lithium sulfate solution obtained in the step S4 to crystallize and precipitate lithium sulfate, and performing solid-liquid separation by using filtering equipment to obtain a wet lithium sulfate semi-finished product, wherein the crystallization mother liquor can be added into the high-concentration lithium sulfate solution obtained in the step S4 for recycling.
Wherein the second organic solvent is one or more of absolute ethyl alcohol, methanol and glycol.
Preferably, the filtration device is selected from a flat-plate scraper centrifuge, a horizontal centrifuge or a vacuum flask.
S6, spray drying: and (5) performing high-temperature spray drying on the lithium sulfate wet product semi-finished product obtained in the step (S5) to obtain a high-purity anhydrous lithium sulfate solid.
Preferably, the spray drying is performed using a spray dryer.
In the technical scheme of the invention, most of the organic solvent can be recycled, the organic phase separated after the first organic solvent is used can be recycled for dissolving lithium sulfate, and the second organic solvent can return lithium to the evaporation concentration step for enrichment, so that closed-loop recycling is formed, residual lithium in the organic phase can be recycled to the maximum extent, the loss and waste of lithium are avoided, and the utilization efficiency of the organic solvent is also improved.
The invention has the beneficial effects that:
the invention provides a method for recovering, extracting and preparing high-purity lithium sulfate solid from mirabilite which is a byproduct of a lithium ore smelting enterprise, which is used for recovering lithium sulfate carried in mirabilite. The method abandons the step of repeated impurity removal, and has simple process flow; other precipitants are not needed to be added, and higher purity can be realized without purification; the solvent can be recycled, and is economical and environment-friendly; the recovery rate of lithium sulfate is high and can reach more than 85 percent. The method of the invention not only achieves the purpose of comprehensively recovering the lithium resource, but also has no three-waste discharge, no pollution to the environment and better economic and social benefits.
Drawings
FIG. 1 is a process flow diagram of the present invention.
The invention is further explained with reference to the drawings and the embodiments.
Detailed Description
Example 1
A method for recovering and extracting high-purity lithium sulfate solid from mirabilite which is a byproduct of a lithium ore smelting enterprise comprises the following specific steps:
s1, dissolving: 300mL of a first organic solvent (a mixture of dichloromethane, petroleum ether and n-butanol, the content of which is 60%, 30% and 10% respectively) and 100g of a byproduct mirabilite solid are stirred and mixed in a 1L beaker, the temperature is 25 ℃, after sufficient stirring for 30 minutes, solid-liquid separation is carried out by using a filter flask, an organic phase containing lithium sulfate as a liquid phase and wet mirabilite as a solid phase are collected, and the wet mirabilite is dried.
S2, washing: and adding the liquid phase obtained in the step S1 into a 1L separating funnel, then injecting 100mL of deionized water, standing for 30 minutes until lithium sulfate ions reach the dissolution balance, allowing most of lithium sulfate to enter the water phase from the organic phase, and performing oil-water separation to obtain the water phase and the organic phase containing lithium sulfate respectively.
S3, circulating: repeating steps S1 and S2, wherein the organic phase obtained in step S2 is used to replace the first organic solvent, and the aqueous phase containing lithium sulfate obtained in step S2 is used to replace the first organic solventIonized water, repeating the steps S1 and S2 three times, enriching the lithium sulfate in the water phase, and finally obtaining Li in the water phase containing the lithium sulfate+The concentration reached 7.7g/L, and the process proceeds to step S4.
S4, evaporation and concentration: heating and evaporating the aqueous phase containing lithium sulfate finally obtained in step S3 at 85 deg.C with a heating plate, and concentrating to obtain Li+Stopping heating after the concentration reaches 20.6g/L, and naturally cooling to obtain a high-concentration lithium sulfate solution which is nearly saturated at normal temperature.
S5, crystallizing: and (3) adding 20mL of a second organic solvent (absolute ethyl alcohol) into the high-concentration lithium sulfate solution obtained in the step S4, rapidly reducing the solubility of lithium sulfate in the water phase to rapidly crystallize and precipitate, performing solid-liquid separation by using a filter flask to obtain a lithium sulfate semi-finished product wet product, and returning the crystallization mother liquor to the step S4 for recycling.
S6, spray drying: and (4) carrying out high-temperature spray drying on the semi-finished lithium sulfate wet product obtained in the step (S5) by using a small spray dryer to finally obtain 6.53g of high-purity anhydrous lithium sulfate solid. Through calculation, the recovery rate of lithium in the whole process flow is 91.95%.
And (3) accurately quantifying the content of the main components in the sample by adopting ICP. The main component indexes before and after mirabilite treatment are as follows: (mass%)
| Na2SO4 | Li+ | K+ | |
| Natrii sulfas before treatment | 43.01 | 0.89 | 0.04 |
| After treatment, mirabilite | 43.77 | 0.07 | 0.03 |
The indexes of the main components of the high-purity anhydrous lithium sulfate solid are as follows: (mass%)
| Li2SO4 | Na+ | K+ | |
| Anhydrous lithium sulfate | 98.47 | 0.64 | 0.01 |
Example 2
A method for recovering and extracting high-purity lithium sulfate solid from mirabilite which is a byproduct of a lithium ore smelting enterprise comprises the following specific steps:
s1, dissolving: 200mL of a first organic solvent (a mixture of dichloromethane, petroleum ether and n-butanol, the content of which is 55%, 35% and 10% respectively) and 100g of a byproduct mirabilite solid are stirred and mixed in a 1L reaction kettle, the temperature is 25 ℃, after sufficient stirring for 30 minutes, solid-liquid separation is carried out by using a suction flask, an organic phase containing lithium sulfate as a liquid phase and wet mirabilite as a solid phase are collected, and the wet mirabilite is dried.
S2, washing: and adding the liquid phase obtained in the step S1 into a 1L separating funnel, then injecting 70mL of deionized water, standing for 30 minutes until lithium sulfate ions reach the dissolution balance, allowing most of lithium sulfate to enter the water phase from the organic phase, and performing oil-water separation to obtain the water phase and the organic phase containing lithium sulfate respectively.
S3, circulating: repeating the steps S1 and S2, wherein the organic phase obtained in the step S2 is used for replacing the first organic solvent, the aqueous phase containing the lithium sulfate obtained in the step S2 is used for replacing the deionized water, the steps S1 and S2 are repeated three times, the lithium sulfate is enriched in the aqueous phase, and finally Li in the aqueous phase containing the lithium sulfate+The concentration reached 8.4g/L, and the process proceeds to step S4.
S4, evaporation and concentration: heating and evaporating the water phase containing the lithium sulfate finally obtained in the step S3 at the temperature of 80 ℃ by using an electric furnace, and finally concentrating to Li+Stopping heating after the concentration reaches 21.2g/L, and naturally cooling to obtain a high-concentration lithium sulfate solution which is nearly saturated at normal temperature.
S5, crystallizing: and (3) adding 15mL of a second organic solvent (methanol) into the high-concentration lithium sulfate solution obtained in the step S4, rapidly reducing the solubility of lithium sulfate in the water phase to rapidly crystallize and precipitate, performing solid-liquid separation by using a filter flask to obtain a lithium sulfate semi-finished product wet product, and returning the crystallization mother liquor to the step S4 for recycling.
S6, spray drying: and (4) carrying out high-temperature spray drying on the semi-finished lithium sulfate wet product obtained in the step (S5) by using a small spray dryer to finally obtain 5.80g of high-purity anhydrous lithium sulfate solid. Through calculation, the recovery rate of lithium in the whole process flow is 88.29%.
The ICP is adopted to accurately quantify the content of the main components in the sample, and the indexes of the main components before and after the mirabilite treatment are as follows: (mass%)
| Na2SO4 | Li+ | K+ | |
| Natrii sulfas before treatment | 43.06 | 0.81 | 0.04 |
| After treatment, mirabilite | 43.68 | 0.09 | 0.03 |
The indexes of the main components of the high-purity anhydrous lithium sulfate solid are as follows: (mass%)
| Li2SO4 | Na+ | K+ | |
| Anhydrous sulfurLithium acid | 96.88 | 1.89 | 0.07 |
Example 3
A method for recovering and extracting high-purity lithium sulfate solid from mirabilite which is a byproduct of a lithium ore smelting enterprise comprises the following specific steps:
s1, dissolving: 100mL of a first organic solvent (a mixture of dichloromethane, petroleum ether and n-butanol, the content of which is 50%, 40% and 10% respectively) and 100g of a byproduct mirabilite solid are stirred and mixed in a 1L beaker, the temperature is 25 ℃, after sufficient stirring for 30 minutes, solid-liquid separation is carried out by using a filter flask, an organic phase containing lithium sulfate and a solid phase which are used as liquid phases are collected, and wet mirabilite is dried.
S2, washing: and adding the liquid phase obtained in the step S1 into a 1L separating funnel, then injecting 40mL of deionized water, standing for 30 minutes until lithium sulfate ions reach the dissolution balance, allowing most of lithium sulfate to enter the water phase from the organic phase, and performing oil-water separation to obtain the water phase and the organic phase containing lithium sulfate respectively.
S3, circulating: repeating the steps S1 and S2, wherein the organic phase obtained in the step S2 is used for replacing the first organic solvent, the aqueous phase containing the lithium sulfate obtained in the step S2 is used for replacing the deionized water, the steps S1 and S2 are repeated three times, the lithium sulfate is enriched in the aqueous phase, and finally Li in the aqueous phase containing the lithium sulfate+The concentration reached 8.9g/L, and the process proceeds to step S4.
S4, evaporation and concentration: heating and evaporating the aqueous phase containing lithium sulfate finally obtained in step S3 at 85 deg.C with a heating plate, and concentrating to obtain Li+After the concentration reached 21.9g/L, the heating was stopped, and the solution was naturally cooled to near saturation at room temperature.
S5, crystallizing: and (3) adding 10mL of a second organic solvent (ethylene glycol) into the concentrated aqueous phase, rapidly reducing the solubility of the lithium sulfate in the aqueous phase to rapidly crystallize and precipitate, performing solid-liquid separation by using a filter flask to obtain a wet lithium sulfate semi-finished product, and returning the crystallized mother liquor to the step S3 for recycling.
S6, spray drying: and (4) carrying out high-temperature spray drying on the semi-finished lithium sulfate wet product obtained in the step (S5) by using a small spray dryer to finally obtain 5.42g of high-purity anhydrous lithium sulfate solid. Through calculation, the recovery rate of lithium in the whole process flow is 85.74%.
The ICP is adopted to accurately quantify the content of the main components in the sample, and the indexes of the main components before and after the mirabilite treatment are as follows: (mass%)
The indexes of the main components of the high-purity anhydrous lithium sulfate solid are as follows: (mass%)
| Li2SO4 | Na+ | K+ | |
| Anhydrous lithium sulfate | 94.46 | 2.76 | 0.09 |
The evaluation of the recovery effect of examples 1 to 3 of the present invention is shown in Table 1.
TABLE 1 evaluation of the recovery Effect of the examples
As can be seen from table 1, the recovery rate and purity of lithium sulfate were the highest in example 1. The first organic solvent and the second organic solvent described in example 1 were subjected to scale-up production to examine whether the method of the present invention is suitable for practical production scale.
Example 4
A method for recovering and extracting high-purity lithium sulfate solid from mirabilite which is a byproduct of a lithium ore smelting enterprise comprises the following specific steps:
s1, dissolving: mixing 300L of first organic solvent (dichloromethane, mixture of petroleum ether and n-butanol, content of 60%, 30% and 10% respectively) and 100kg of byproduct Natrii sulfas solid under stirring at 1m3The reaction kettle is stirred for 30 minutes at the temperature of 25 ℃, solid-liquid separation is carried out by using a centrifugal machine, an organic phase containing lithium sulfate as a liquid phase and wet mirabilite as a solid phase are collected, and the wet mirabilite is dried.
S2, washing: to 1m3Adding the liquid phase obtained in the step S1 into the reaction kettle, then injecting 100L of deionized water, standing for 30 minutes until lithium sulfate ions reach the dissolution balance, allowing most of lithium sulfate to enter the water phase from the organic phase, and performing oil-water separation by using a centrifugal oil-water separator to obtain the water phase and the organic phase containing lithium sulfate respectively.
S3, circulating: repeating the steps S1 and S2, wherein the organic phase obtained in the step S2 is used for replacing the first organic solvent, the aqueous phase containing the lithium sulfate obtained in the step S2 is used for replacing the deionized water, the steps S1 and S2 are repeated three times, the lithium sulfate is enriched in the aqueous phase, and finally Li in the aqueous phase containing the lithium sulfate+The concentration reached 7.9g/L, and the process proceeds to step S4.
S4, evaporation and concentration: adding the aqueous phase containing lithium sulfate finally obtained in step S3 at a temperature of 85 ℃ using a triple effect evaporatorThermal evaporation, final concentration to Li+Stopping heating after the concentration reaches 20.3g/L, and naturally cooling to obtain a high-concentration lithium sulfate solution which is nearly saturated at normal temperature.
S5, crystallizing: and (3) adding 20L of a second organic solvent (absolute ethyl alcohol) into the high-concentration lithium sulfate solution obtained in the step (S4), rapidly reducing the solubility of lithium sulfate in the water phase to rapidly crystallize and separate out, performing solid-liquid separation by using a horizontal centrifuge to obtain a lithium sulfate semi-finished product wet product, and returning the crystallization mother liquor to the step (S4) for recycling.
S6, spray drying: and (4) carrying out high-temperature spray drying on the semi-finished lithium sulfate wet product obtained in the step (S5) by using a spray dryer to finally obtain 6.77kg of high-purity anhydrous lithium sulfate solid. Through calculation, the recovery rate of lithium in the whole process flow is 92.38%.
And (3) accurately quantifying the content of the main components in the sample by adopting ICP. The main component indexes before and after mirabilite treatment are as follows: (mass%)
| Na2SO4 | Li+ | K+ | |
| Natrii sulfas before treatment | 42.94 | 0.92 | 0.04 |
| After treatment, mirabilite | 43.79 | 0.07 | 0.03 |
The indexes of the main components of the high-purity anhydrous lithium sulfate solid are as follows: (mass%)
Finally, it should be emphasized that the above-described preferred embodiments of the present invention are merely examples of implementations, rather than limitations, and that many variations and modifications of the invention are possible to those skilled in the art, without departing from the spirit and scope of the invention.
Claims (9)
1. A method for extracting and preparing high-purity anhydrous lithium sulfate solid from mirabilite which is a byproduct of a lithium smelting enterprise is characterized by comprising the following steps:
s1, dissolving: adding mirabilite and a first organic solvent into a container, fully stirring, performing solid-liquid separation by using a filtering device, respectively collecting a solid phase and a liquid phase, wherein the liquid phase is an organic phase containing lithium sulfate, the solid phase is wet mirabilite, and drying the wet mirabilite;
s2, washing: injecting deionized water into the liquid phase obtained in the step S1, standing, and separating by using oil-water separation equipment to obtain a water phase and an organic phase containing lithium sulfate respectively;
s3, circulating: repeating steps S1 and S2, wherein the organic phase obtained in step S2 is used to replace the first organic solvent, the aqueous phase containing lithium sulfate obtained in step S2 is used to replace the deionized water, and the above steps are repeated until Li in the aqueous phase containing lithium sulfate+When the concentration is not increased any more, the next step is carried out;
s4, evaporation and concentration: heating, evaporating and concentrating the water phase containing the lithium sulfate finally obtained in the step S3 by using evaporation equipment to obtain a high-concentration lithium sulfate solution;
s5, crystallizing: adding a second organic solvent into the high-concentration lithium sulfate solution obtained in the step S4 to crystallize and separate out lithium sulfate, and performing solid-liquid separation by using filtering equipment to obtain a lithium sulfate wet product semi-finished product and a crystallization mother liquor, wherein the crystallization mother liquor can be added into the high-concentration lithium sulfate solution obtained in the step S4 for recycling;
s6, spray drying: and (5) performing high-temperature spray drying on the lithium sulfate wet product semi-finished product obtained in the step (S5) to obtain a high-purity anhydrous lithium sulfate solid.
2. The method of claim 1, wherein: in the step S1, the first organic solvent is a mixture of dichloromethane, petroleum ether and n-butanol, the content range of dichloromethane in the mixture is 40% -70%, the content range of petroleum ether is 30% -60%, and the content range of n-butanol is 5% -40%.
3. The method of claim 2, wherein: the mixture contained 60% of dichloromethane, 30% of petroleum ether and 10% of n-butanol.
4. The method of claim 1, wherein: the filtering device in the step S1 is selected from a plate and frame filter, a centrifuge or a vacuum flask.
5. The method of claim 1, wherein: the oil-water separation device in the step S2 is selected from a centrifugal oil-water separator, a vacuum filtration oil-water separator, or a separatory funnel.
6. The method of claim 1, wherein: the evaporation apparatus in step S4 is selected from a triple effect evaporator, MVR or hot plate.
7. The method of claim 1, wherein: step S4 is to concentrate the aqueous phase containing lithium sulfate to Li+The concentration range is 18-28 g/L.
8. The method of claim 1, wherein: the second organic solvent in step S5 is one or more of absolute ethanol, methanol, or ethylene glycol.
9. The method of claim 1, wherein: the filtering device in step S5 is selected from a flat-plate scraper centrifuge, a horizontal centrifuge or a vacuum flask.
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| CN101851266A (en) * | 2010-05-06 | 2010-10-06 | 沈阳药科大学 | Novel cycloartane triterpenoidsaponins and preparation method and application thereof |
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